US2313586A

US2313586A - Hydroxynaphthoic acid amide coupler

Info

Publication number: US2313586A
Application number: US361262A
Authority: US
Inventors: Ilmari F Salminen; Dudley B Glass
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1939-08-24
Filing date: 1940-10-15
Publication date: 1943-03-09
Anticipated expiration: 1960-03-09
Also published as: US2298443A; GB536939A; FR932002A

Description

Patented Mar. 9, 1943 Q I j 2,313.586

UNITED STATES PATENT. OFFICE Ilmari F. Sahninen, Arnold Weissherger, and Dudley B. Glass, Rochester. N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application October 15, 1940, Se-

rial No. 361,262. In Great Britain February 20, 1940 4 Claims. (CI. 95-88) This invention relates to color-forming devel- 'ble to heat and light than the corresponding opment and particularly to novel coupling comamides derived from primary amines. ponents for producing colored images. The compounds which we propose to use have It is known that colored photographic images 'the following formula: may be formed by using a developer which forms 5 0 a colored compound on development. The colored compound thus formed is deposited adja- R cent to the silver grains of the silver image dur- 0 ing the development. It is also known that a colored image may be formed, by adding to certain developer solutions or by incorporating in V the gelatino-silver-halide emulsion before or aftw i d R'=a,1ky1, aryl, aralkyl.

er exposure a compound which couples during de- Specific compounds which may be used velopment with the oxidation product of the cording t our i v ti n are the following:

developing agent and forms a coloring substance V I which is likewise deposited adjacent to the silver Cm grains of the silver image during development. I

Such a compound, which is employed in conjunc- I O tion with a developing agent for the silver and v v which couples with the oxidation product thereof 2 during development, is referred to herein as a I.

coupling component or coupler. Y l'hydmxy'zmphmic'N'mthylHide The present invention concerns new or improved color forming developers comprising a l 02m primary aromatic amino compound, serving as (2) (F111 the developing agent, and a coupler as hereinafter defined and also includes a new or improved color development process which consists in de- 7 veloping a reducible silver salt image in a photo- 1 h d xy-?,(N-ethy1, N-s-mphthyl) naphth mlde graphic element with the aid of a primary aromatic amino compound in the presence of a cou- 0H pler as hereinafter defined. It also includes pho- I CnHn tographic sensitive elements having such a coupler incorporated in one or more emulsion layers. In British Patent 503,752 carboxylic acid amide couplers are described which are obtained by the reaction of a-naphthol carboxylic acid chloride with amines containing a high molecular substituent group. In these couplers the hy- OH droxyl group of the naphthol constitutes the di- 40 3 0 recting group inthe coupling reaction. and the a 00 N I carbon atom of 'the carboxylic acid amide group (4) is, therefore, directly attached to the coupler porf OWE;

tion of the molecule, and the amide may be con-' sidered as being derived from a primary amine. 5

While these compounds form colored photo- (a) CO-N graphic images upon development in primary 1 hydroxy MN iilfilfi' ilnfifii aromaticramino developers, the coupler molecule J 0H p in certain cases is unstable to heat and light I cmcmcgro and is unsatisfactory for that reason. (5) c We'have found. that hydrcxynaphthoic acid amide couplers in which the amide may be con-- 7 Q sidered as being derived from a secondary amine possess more desirable light absorption charac- 1J1 dm he l h teristics for color photography and are more statiiifi my!) mph l-hydrory 2-(N-amyhN-a-naphthyhnaphthamide l-hydroxy-2-(N-i5obutyi N-p-amylbenzene) naphthai'nide CsHu t 9 wee-N cm co-zi-O 4o N-methyl-5-hydroxymphthanilidc i-hydroxy-Z-(N-isobutyl-N-psoc-amylbcnzmc)-naphtliamide l-hydroxy-fl-(N-banzyi-N-lp-swwamyll bcmne)-naphthamide 65 i-hydrouy-a-(N-n-cmyl-N-emphthyb-mphmidc I 75 in. cmcmcn.

CHr- H-CH2CH:CH3 l-hydroxy-2-(N-n-amyl-N-psec.-amylbenzene)-naphthamide C O-N C HaC H2O H:- C Ha-lH-CHaC HrCHs 7 l-hydroxy-2-(N-[ -pheny1]pr6py1-N-p-sec.-amylbonzene) naphtham his c O-N-CHIC morn-O 5'-hydroxy-l-(N-phenyl-Nfi-phenyl-propyl)-naphtharnide The couplers may be prepared by the reaction of secondary amines withthe acid chlorides of hydroxynaphthoic acids, with the acid chlorides 01 their esters and subsequent hydrolitic elimination of the acid groups, or with their esters. These reactions can also be applied to the substitution products of the hydroxynaphthoic acids with suitable substituents in one or both rings or the reaction products can be substituted, for example, with chlorine. The couplers made according to our invention may be dissolved in the developing solution or may be incorporated in the emulsion layer according to their solubility characteristics. Compounds 2 to 9 and 11 to 16 are suitable for use in the emulsion layer and the remaining compounds are sufllciently soluble for use in the developing solution. The use of an alcohol in the developer which is a solvent for the coupler improves the color produced particularly when the coupler is in the layer.

These couplers contain a phenolic hydroxyl group which is reactive with the oxidation prod-v uct of a primaryaromatic amino coupling developing agent to form colored images. The compounds are presumably active in the ortho or para position with respect to-the position of the hydroxyl group.

The coupling compounds used according to our invention may contain other substituents which do not affect the coupling properties of the compound. For example, the naphthol portion of the coupler may contain substituent groups and may even contain readily replaceable groups such as chlorine or bromine in the position ortho or' para with respect to the hydroxyl group where such substituents do not affect the coupling prop erties. Where we refer in the general formula to aryl and-aralkyl groups, it is to be understood I that these groups maybe further substituted.

The aromatic amino developing agents used with the coupler compounds of our'invention include the mono-, diand tri-aminoarylcompounds and their derivatives formed by substitution in the amino group as well as in the ring, such as alkylphenylenediamines and alkyltoluylenediamines. These compounds are usually used in the salt form, such as the hydrochloride or the sulfate, which are more stable than the amines themselves. Suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediaminehydrochloride and dimethyl-p-phenylenediamine sulfate. The paminophenols and their substitution products may also be used where the amino group is substituted. All of these compounds have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color forming compounds to form a dye image.

The following developer formula may be used with the compounds of our invention:

A; p-Aminodiethylaniline sulfate grams 2 Sodium sulfite anhydrous do, 5 Sodium carbonate anhydrous do 20 Potassium bromide do. 2 Water to liter 1 B. Coupler "grams-.. 1to5 Isopropyl alcohol -cc 100 Bisadded toA.:

In case the coupler isincorporated in the emulsion layer, the alcohol in the developer acts as a solvent for the coupler and improves the color. Our development process may be'employed'for the production of colored photographic images in layers of gelatin or other carrier such as collodion, organic esters of cellulose or synthetic resins. The carrier may be supported by a transparent medium such as glass, a cellulose ester, or a non-transparent reflecting medium such as paper of an opaque cellulose ester. The emulsion may be coated as a single layer on the support or as superposed layers on one or both sides of the support. The superposed layers may be diflerentially sensitized to formznatural color photographic images in the well known manner.

The examples and compounds set forth in the present specification are illustrative only and it is to be understood that our invention is limited only by the scope of the appended claims.

We claim:

1. A color forming photographic developer comprising a primary aromatic amino developing agent and a coupler compound having the formula:

' where R is an aryl radical and R is an aralkyl radical. 1

2. The method of producing a colored photographic image in a gelatino silver halide emulsion layer which comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:

. on I CON\ where R is an aryl radical and R is an arallryl radical.

3. A color-forming photographic developer or:v

I CON\ R,

where R is an aryl radical and R is an aralkyl radical.

4. The method of producing a. colored photographic image in a gelatino-silver halide emulsion layer which comprises exposing the layer and developing it with a primary aromatic amino developing. agent in the presence of a coupler compound having the formula:

/R v CON\ I radical.

aryl radical and R. is an aralkyl